N-trihalovinylmercaptophthalimides



United States Patent Ofiice Patented Jan. 30, 1968 This is acontinuation-an-part of copending application S.N. 852,931. now U.S.Patent No. 3,296,302.

This invention relates to novel compositions of matter and the novelanti-microbial uses thereof. More particularly, this invention relatesto N-t-rihalovinylmercaptophthalimide and the use thereof as a means forcontrolling microbes.

In accordance with this invention, there is provided N-trihalovinylmercaptophth-alimide. There is further provided a method forthe control of microbes, which comprises applying to the locus to betreated an efiective amount of N-trih-alovinylmercaptophthalimide.

The compounds of this invention may be prepared by reacting triandtetrahal-ovinylsulfenyl halide with phthalimides. Saidtrihalovinylsulfenylhalides may be characteriz'ed by the formula whereinX is a halogen such as fluorine. chlorine, bromine, or iodine,preferably chlorine or bromine. Some of the trih-alovinylsulfenylhalides which may be used to prepare the compounds of this inventionare, e.g., trichlorovinylsulfenylchl'oride, trichlorovinylsulfenylbromides, bromodichlorovinylsulfenyl chlorides,dibromochlorovinylsulfenyl bromides, tribromovinylsulfenyl chloride,tribromovinylsulfenyl bromide, and the like.

Said trihalovinylsulfenylhalides, while stable per se, are reactive withmany substances, including oxygen and oxidizing agents such as nitricacid and hydrogen peroxide (with which they form the correspondingsulfinic and sulfonic derivatives); with chlorine and bromine (withwhich they form pentahalosulfenyl halides); with nucleophilic anions(which, generally, first replace the halogen on the sulfur atom); withnitrogen bases bearing a replaceable hydrogen or metal on the nitrogenatom (which bases generally replace the halogen on the sulfur atom witha nitrogen-containing radical); with reducing agents such as hydriodicacid (with which they generally form the disulfide corresponding to thesulfenyl chloride); with aromatic compounds (to form trichlorovinyl'aryl sulfides), with olefins, such as, e.g., unsaturated resins andunsaturated natural oils (with which they form 2-haloalkyl sulfides);with acetylenes (with which they form 2- -halovinyl sulfides); withhydrogen sulfides (with which they form triand polysulfidescorresponding to the sulfenyl halide); with organic phosphites (withwhich they form, inter alia, S-trihalovinylphosphorothiolates; and withcarbanions (with which they form trihalovinyl alkyl sultides).

Said trihalovinylsulfenylhalides are preferably synthesized either bythe dehydrohalogenation of tetrahaloethylsulfenyl halides or by thechloroinolysis of trihalovinyl disulfides (or higher polysulfides).Sulfenyl bromides may also be prepared from the sulfenyl chlorides byhalogen exchange methods such as the reaction of hydrogen bromide withthe sulfenyl chloride.

Tric-hlorovinylsulfenyl chloride may be prepared, for example, bychlorinolysis of bis(trichlorovinyl) disulfide.Dichlorobromovinylsulfenyl may be prepared by chlorinolysis ofbis(dibromochlorovinyl) dislufide. Dibromochlorovinylsulfenyl chloridemay be prepared by the chlorinolysis of bis(dibromochlorovinyl)disulfide. If trisulfides or higher polysulfides are used, sulfurchlorides are formed as by-products. Monosulfides do not undergo thischlorinolysis reaction. The chlorinolyis may, if desired, be acceleratedby the use of catalysts such as iodine or Lewis acids.

Said trihalovinylsulfenylhalides, when reacted with phthalimide, willform the compounds 'of this invention, as illustrated by the reactionshown below:

N-trihalovlnylmercaptophthallmlde The compounds of this invention mayalso be prepared by reacting phthalimide with tetrahaloethylsulfenylhalide in the presence of a tertiary amine, in which casedehydrohalogenation in situ occurs and the desiredN-trihalovinylmercapt-o phth-alimide is obtained.

In general, any ehlorocarbo-n, aromatic, or hydrocarbon solvent may beused for the aforementioned process, though it is preferred to usechlorocarbon solvents. Some of the more preferred solvents include,e.g., chloroform, methylene chloride, carbon tetrachloride,trichloroethylene, perchloroethylene, and the like.

Any tertiary amine is operative in said process. Some of the amineswhich may be used in said processes include trialkylamines, such astrimethylamine, triethylamine, tributylamine, and the like;diethylcyclohexylamine; diethylethanolamine; N-diethylaminoacetic acid;methyliminodipropionic acid; dimethyl-aminopropionitrile;.Nnnethyl'dipropyttriamine; dimethyl (2 methoxyethyl) amine;'diethyl(ethoxyethoxy-propyl)amine; dirnethylpirperazine;-N-(Z-methoxyethyl)piperidine; p-bis(-N-diethylaminoethyl-paphenyleneether; and the like. It is to be understood that any tertiary amine willwork in said processes, and that the above list of amines is merelyexemplary.

In said processes, about 1:1 molar ratio of phthalimide: sulfenyl halideis used, though either of said reactants may be used in excess.

During the reaction of the sulfenyl halide and the phthalimide, thereaction mixture should be maintained at a temperature of from about 35vdegrees oentigrade to about degrees centigrade, though it is preferredto have the reaction mixture at a temperature of from about 0 to about70 degrees centigrade, and it is even more preferred to have saidtemperature at from about 10 degrees centigrade to about ambienttemperature.

The compounds of this invention are anti-microbial. When used, e.g., tocontrol soil pathogens, such as Pythium, said compounds may be employedat an application rate of from about 0.5 to about 200 pounds per acre,the preferred rate being dependent upon the soil to be treated, thepathogen and crop involved, and other fac tors Well known to thoseskilled in the art of soil disinfestation, though it is generallypreferred to use an aplication rate of from about 2 to about 100 poundsper acre. When used, e.g., to control foliar fungi such as Alternariasolani, said compounds may be applied to the locus to be treated at aconcentration of from about to about 500,000 parts of compound permillion parts of carrier, though it is generally preferred to use aconcen tration of from about 50 to about 50,000 parts per million. Whenused to control bacteria such as Staphylococcus aureus (Gram saidcompounds may be applied to the locus to be treated at a concentrationof about 1 to 10,000 parts per million parts of carrier, though it ispreferred to use a concentration of from about 10 to 1000 parts permillion.

In a preferred embodiment of this invention, X is selected from thegroup consisting of chlorine and bromine. In an even more preferredembodiment of this invention, X is chlorine.

The following examples are illustrative of the invention and are not tobe deemed limitative thereof. Unless otherwise specified, parts are byweight and temperatures are in degrees Centigrade.

EXAMPLE 1 To 29 parts of bis(trichlorovinyl)disulfide were added 6.3parts of chlorine at a temperature of degrees Centigrade. The mixturewas allowed to warm slowly to room temperature, and then was distilledthrough a short fractionating column, yielding 27 parts oftrichlorovinylsulfenyl chloride, a red, malodorous liquid boiling at3945 degrees centigrade at (0.3-0.5 millimeter of mercury pressure). Theinfrared spectrum showed the presence of a double bond at 6.55 m Thepresence of the sulfenyl function was proved by the release of iodinefrom potassium iodide solution immediately upon admixture of the productwith said solution. Elemental analysis revealed that the product wascomprised of 72 percent chlorine and 15.7 percent sulfur, indicatingthat it was trichlorovinylsulfenyl chloride, which has a theoreticalchlorine content of 71.8 percent and a theoretical sulfur content of15.7 percent.

EXAMPLE 2 23.5 parts of tetrachloroethylsulfenyl chloride were dissolvedin 30 parts of chloroform, said dissolution occurring at a temperatureof 20 degrees centigrade. To this solution was added a solution of 10parts of triethylamine in 120 parts of chloroform. This mixture wasallowed to stand for four hours, at which time it was quickly washedwith cold water and rapidly stripped under water pump vacuum to yield 18parts of trichlorovinylsulfenyl chloride, which, upon infrared analysis,exhibited the same spectrum as did the product of Example 1.

EXAMPLE 3 14.6 parts of phthalimide and 10.1 parts of triethylamine weredissolved in 120 parts of chloroform, said dissolution occurring at atemperature of 20 degrees centigrade. To this solution was added 20parts of trichlorovinylsulfenyl chloride. The mixture was stirred forfour hours, at which time it was quickly washed with cold water (toremove triethylamine hydrochloride), evaporated to about one-halfvolume, and filtered to remove unreacted phthalimide. The filtrate wasevaporated to dryness, and was then recrystallized from carbontetrachloride to yield 13 parts of light-tan, crystalline product with amelting point of 133- 135 degrees centigrade and having the correctchlorine analysis for N-trichlorovinylmercaptophthalimide. Elementalanalysis also revealed the product was comprised of 4.54 percentnitrogen; theoretical nitrogen content forN-trichlorovinylmercaptophthalim'ide is 4.76 percent.

EXAMPLE 4 A solution of 23.5 parts of tetrachloroethylsulfenyl chloridein 30 parts of chloroform was added over a period of 15 minutes to asolution of 14.6 parts of phthalimide, 20.2 parts of triethylamine, andparts of chloroform. During said addition the temperature of thereaction mixture was about 20 degrees centigrade. Thereafter, thereaction mixture was cooled to about 10 degrees centigrade, whichcooling caused the precipitation of 2.8 parts of unreacted phthalimide,which was removed from the reaction mixture. The remaining solution wasevaporated to about one-half volume, and then cooled to yield 9.6 partsof a solid with a melting point of 124-128 degrees centigrade. Saidsolid was recrystallized from heptane, and yielded a light-tancrystalline product with a melting point of 133-135 degrees centigrade.Elemental analysis indicated that said product was comprised ofN-trichlorovinylmercaptophthalimide.

EXAMPLE 5 To a solution of 302 parts of tetrahydrophthalimide, 44.4parts of triethylamine, and parts of chloroform was added 51.7 parts oftetrachloroethylsulfenyl chloride. Said addition occurred at roomtemperature, and was made over a period of one hour. After said additionthe reaction mixture was concentrated on a steam bath under reducedpressure. The resulting mixture Was washed with water, and from saidmixture was extracted 39.3 parts of triethylamine hydrochloride. Themixture from which said triethylamine hydrochloride had been extractedwas separated into two fractions, each of which had a differentsolubility in ethyl ether. The less soluble fraction (-M.P. degreescentigrade) was heated at 100 degrees centigrade/ 0.25 millimetersvacuum in a sublimation apparatus, and a small amount of said fractionsublimed. The residue, after elemental analysis thereof, was discoveredto have 9.2 percent sulfur and 4.15 percent nitrogen, indicating thatsaid residue was comprised ofN-trichlorovinylmercaptotetrahydrophthalimide.

EXAMPLE 6 The procedure of Example 4 was essentially followed, with theexception that 22.2 parts of triethylamine and 23.5 parts oftetrachlorovinylsulfenyl chloride were used. The chloride determinationof the washings of the reaction ixture indicated the presence of 27.4parts of triethylamine hydrochloride, indicating the product was comprised of N-trichlorovinylmercaptotetrahydrophthalimide in as much asthe theoretical amount of triethylamine hydrochloride is 30.0 parts.

EXAMPLES 7 AND 8 In Examples 7 and 8, the products of Examples 3 and 4were tested to determine whether they possessed antimicrobial activity.The following test methods were used:

Bactericidal test The bacteria were grown on agar slants for 20 hours.To a mixture of the chemical to be tested and nutrient agar were addedtwo drops of the bacterial suspension, and this mixture was shaken andthen poured onto sterilized Petri plates. The plates were incubated for24 hours and the bacterial growth noted.

Spray tests (fungicides)early blight Tomato plants were sprayed with 100milliliters of the chemical to be tested, dried, inoculated with sporesof Allernaria solani, and incubated in a moist chamber at 70 degreesFahrenheit for 24 hours. Control plants were not sprayed with thechemical. Percent control was determined by the formula:

Per Cent Control (number of spots which develop on leaves of untreatedtomato plant-number of spots which develop on leaves of treated plant) X1.00

number of spots which develop on leaves of untreated plant Soilfungicide testsPythium Soil naturally infested with Pythium species wastreated with the chemical solution to be tested and allowed to stand 3days before planting. Plastic pots 3.5 X 3.0 inches were filled with thesoil, and the chemical applied to the soil therein by drenching. After 3days, ten pea seeds, Perfection variety, were planted in each pot.Percent emergence was recorded.

EXAMPLE 9 The product of Example 3, N-trichlorovinylmercaptophthalimide,exhibited 10, 46, 94, 96, and 100 percent control of Alternaria solaniat concentrations of 20, 25, 50, 80, 160 and 320 parts per million,respectively. Said N-trichlorovinylmercaptophthalimide exhibited 20, 80and 100 percent control of Pythium at application rates of 16, 32, and64 pounds per acre, respectively (i.e., at an application rate of 32pounds per acre of N-trichlorovinylmercaptophthalimide, 80 percent ofthe pea seeds planted in the Pythium-infested soil emerged). At aconcentration of 38 parts per million, complete control of the bacteriaStaphylococcus aureus was obtained.

When bromodichlorovinylmercaptophthalimide ordibromochlorovinylmercaptophthalimide is used instead ofN-trichlorovinylmercaptophthalimide, similar results are obtained.

EXAMPLE 10 The product of Example 4, exhibited 51, 79, 84, 98 and 100percent control of Alternaria solani at concentrations of 25, 80, 100and 160 and 320 parts per million, respectively. At an application rateof 64 pounds per acre, 20 percent control of Pythium was exhibited. At aconcentration of 255 parts per million, complete control ofStaphylococcus aureus was obtained.

-When tribromovinylmercaptotetrahydrophthalimide is used instead of Ntrichlorovinylmercaptotetrahydrophthalimide, similar results areobtained.

While the invention has been described with reference to certainspecific embodiments, it will be recognized by those skilled in the artthat many variations are possible Without departing from the spirit andscope of the invention.

What is claimed is:

1. A compound of the formula References Cited UNITED STATES PATENTS10/1964 Aichenegg et al 260-301 10/1964 Aichenegg et a1. 16733 ALEXMAZEL, Primary Examiner. J. A. NARCAVAGE, Assistant Examiner.

1. A COMPOUND OF THE FORMULA